U.S. patent number 4,024,117 [Application Number 05/569,739] was granted by the patent office on 1977-05-17 for hydrocurable compositions of hydroxy(polyalkylenecarbonyloxy)-alkyleneoxazolidine and an isocyanate.
This patent grant is currently assigned to Rohm and Haas Company. Invention is credited to William D. Emmons.
United States Patent |
4,024,117 |
Emmons |
May 17, 1977 |
Hydrocurable compositions of
hydroxy(polyalkylenecarbonyloxy)-alkyleneoxazolidine and an
isocyanate
Abstract
Hydrocurable compositions of a
hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidine and a
polyfunctional isocyanate are disclosed. The compositions are
useful in forming films, paints, coatings, fibers, seamless
flooring, coatings, impregnants and adhesives for natural and
synthetic materials. The compositions are prepared by treating a
hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidine with a
polyfunctional isocyanate or by treating a bisoxazolidine
isocyanate prepolymer with a polyfunctional isocyanate.
Inventors: |
Emmons; William D. (Huntingdon
Valley, PA) |
Assignee: |
Rohm and Haas Company
(Philadelphia, PA)
|
Family
ID: |
27026540 |
Appl.
No.: |
05/569,739 |
Filed: |
April 21, 1975 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
425007 |
Dec 14, 1973 |
3912691 |
|
|
|
Current U.S.
Class: |
528/69; 528/73;
548/215; 548/216 |
Current CPC
Class: |
C07D
263/22 (20130101); C07D 265/06 (20130101); C08G
18/3296 (20130101); C08G 18/4269 (20130101); C08G
18/4646 (20130101); C08G 63/6852 (20130101) |
Current International
Class: |
C08G
18/32 (20060101); C07D 263/00 (20060101); C07D
263/22 (20060101); C07D 265/06 (20060101); C07D
265/00 (20060101); C08G 63/00 (20060101); C08G
63/685 (20060101); C08G 18/00 (20060101); C08G
18/42 (20060101); C08G 18/46 (20060101); C08G
063/02 () |
Field of
Search: |
;260/78.3R,37F,37FA |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Welsh; M. J.
Attorney, Agent or Firm: Strobaugh; Terence P. Simmons;
George W. F. Doherty; Robert A.
Parent Case Text
This is a division of application Ser. No. 425,007, filed Dec. 14,
1973, and now U.S. Pat. No. 3,912,691.
Claims
What is claimed is:
1. A compound of the formula: ##STR7## wherein R.sup.1 is hydrogen,
mononuclear aryl, aralkyl or alkyl; R.sup.2 is hydrogen or alkyl or
R.sup.1 and R.sup.2 are joined together with the carbon atom to
which they are attached to form cycloalkyl; R.sup.3 is hydrogen,
alkyl, cycloalkyl, alkoxy or mononuclear aryl; R.sup.1, R.sup.2 and
R.sup.3 may be substituted with halo, lower alkoxy, hydroxy, amino
or nitro; Y is unsubstituted or substituted lower alkylene; X is
substituted or unsubstituted lower alkylene; n is an integer of at
least 4; z is an integer of 1-50 and Z is a polyvalent organic
isocyanate residue.
2. A compound according to claim 1 of the formula: ##STR8## wherein
R.sup.4 is hydrogen or lower alkyl; z' is an integer of 5-20 and Z
is a polyvalent organic isocyanate residue.
3. A compound of the formula: ##STR9## wherein R.sup.1 is hydrogen,
mononuclear aryl, aralkyl or alkyl; R.sup.2 is hydrogen or alkyl or
R.sup.1 and R.sup.2 are joined together with the carbon atom to
which they are attached to form cycloalkyl; R.sup.3 is hydrogen,
alkyl, cycloalkyl, alkoxy or mononuclear aryl; R.sup.1, R.sup.2 and
R.sup.3 may be substituted with halo, lower alkoxy, hydroxy, amino
or nitro; Y is unsubstituted or substituted lower alkylene; X is
substituted or unsubstituted lower alkylene; n is an integer of at
least 4, z is an integer of 1-50, Z is a polyvalent organic
isocyanate residue and m is an integer equal to the valence of
Z.
4. A compound according to claim 3 having the formula: ##STR10##
wherein R.sup.4 is hydrogen or lower alkyl; z' is an integer of
5-20, Z is a polyvalent organic isocyanate residue, and m is an
integer of two or three.
5. A compound of the formula: ##STR11## wherein R.sup.1 is
hydrogen, mononuclear aryl, aralkyl or alkyl; R.sup.2 is hydrogen
or alkyl or R.sup.1 and R.sup.2 are joined together with the carbon
atom to which they are attached to form cycloalkyl; R.sup.3 is
hydrogen, alkyl, cycloalkyl, alkoxy or mononuclear aryl; R.sup.1,
R.sup.2 and R.sup.3 may be substituted with halo, lower alkoxy,
hydroxy, amino or nitro; Y is unsubstituted or substituted lower
alkylene; X is substituted or unsubstituted lower alkylene; n is an
integer of at least 4 and z is an integer of 1-50.
6. A compound according to claim 5 of the formula: ##STR12##
wherein R.sup.4 is hydrogen or lower alkyl and z' is an integer of
5-20.
Description
This invention relates to a novel composition comprising a
hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidine and a
polyfunctional aliphatic or aromatic isocyanate which has an
outstanding balance of speed of cure relative to its stability. The
composition cures in the presence of moisture to afford tough
chemically resistant polymeric materials. This invention also
relates to the novel
hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidines and
bisoxazolidine isocyanate prepolymers.
The reaction of isocyanates with active hydrogen compounds such as
amines and alcohols to form polyureas and polyurethanes has been
greatly studied in the prior art, and this general class of
polymers has been found to possess many useful properties. Since
isocyanates generally react quickly and efficiently with active
hydrogen compounds at room temperature, these two components
usually must be mixed together only at the time and place at which
reaction is desired. In previous approaches to making "one pot"
compositions, in which the reacting materials are packaged together
before using and later activated, relatively unreactive derivatives
of isocyanates have been employed which regenerate the free
isocyanate upon heating. Various catalysts are also often contained
in these compositions to facilitate the regeneration of isocyanate.
However, the heating process has several disadvantages, especially
when the polyurea or polyurethane is to be used as a coating. For
example, the size of the article to be coated or the nature of the
material of which the article is made may preclude heating to the
temperature necessary for polymerization to occur. Thus, it is
extremely desirable to have polymer forming compositions which are
stable on storage and which can be cured in the absence of any
extensive heating and without the specific addition of other
materials. Moreover, polyurea or polyurethane forming compositions
having improved cure times would also be quite valuable.
It has now been found that compositions comprising a
hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidine and a
polyfunctional aliphatic or aromatic isocyanate will cure in the
presence of water such as atmospheric moisture to afford tough and
useful polymeric materials.
The hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidines (I, infra)
employed in the novel hydrocurable compositions of this invention
have the following structural formula: ##STR1## wherein R.sup.1 is
hydrogen, mononuclear aryl, for example, phenyl and the like,
aralkyl, for example, benzyl and the like or alkyl, for example,
alkyl of from 1-12 carbon atoms such as methyl, ethyl, n-propyl,
n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl and the like; R.sup.2 is hydrogen or alkyl, for example,
lower alkyl of from 1-4 carbon atoms such as methyl, ethyl,
n-propyl, n-butyl and the like; or R.sup.1 and R.sup.2 are joined
together with the carbon atom to which they are attached to form
cycloalkyl of from 5-6 carbon atoms, such as cyclopentyl,
cyclohexyl and the like; R.sup.3 is hydrogen, alkyl, cycloalkyl,
alkoxy or mononuclear aryl; Y is unsubstituted or substituted lower
alkylene such as ethylene or propylene, wherein the substituents
may be one or more radicals selected from alkyl, for example, alkyl
of from 1-12 carbon atoms, aryl of 6-10 carbon atoms, aralkyl or
alkanoyl of 7-12 carbon atoms. The R.sup.1, R.sup.2 and R.sup.3
radicals may be further substituted with halo such as chloro,
fluoro, bromo and the like, lower alkoxy, such as methoxy, ethoxy
and the like, hydroxy, amino or nitro; X is substituted or
unsubstituted lower alkylene such as ethylene, propylene, butylene
and the like, wherein the substituent may be one or more alkyl
radicals, for example, lower alkyl of from 1-6 carbon atoms; n is
an integer of at least 4, for example, 4-6, and z is an integer of
1-50.
A wide variety of polyfunctional isocyanates, that is, isocyanates
having at least two NCO groups, can be used in the compositions of
the invention and substantially any isocyanate having two or more
NCO groups which will react with an oxazolidine in the presence of
moisture can be used. The isocyanates which are used in the
compositions of the invention are well-known in the art.
Examples of the polyisocyanates which can be used in the
compositions of the invention are aliphatic diisocyanates such as a
diisocyanate derived from a 36 carbon diamine (DDI - General Mills,
Inc.), 1,6-hexamethylene diisocyanate, 1,8-octamethylene
diisocyanate, 1,12-dodecamethylene diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate, and similar alkylene
diisocyanates, 3,3'-diisocyanatodipropyl ether,
3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate,
cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate,
methyl 2,6-diisocyanatocaproate, and related isocyanates,
bis(2-isocyanatoethyl)fumarate,
4-methyl-1,3-diisocyanatocyclohexane, trans-vinylene diisocyanate
and similar unsaturated isocyanates,
4,4'-methylene-bis(isocyanatocyclohexane), and related isocyanates,
menthane diisocyante,
N,N',N"-tris(6-isocyanatohexamethylene)biuret, and related
isocyanates, bis(2-isocyanatoethyl)carbonate, and similar carbonate
diisocyanates, as well as other known isocyanates derived from
aliphatic polyamines, aromatic isocyanates such as tolylene
diisocyanates, xylylene diisocyanates, dianisidine diisocyanate,
4,4'-diphenylmethane diisocyante, 1-ethoxy-2,4-diisocyanatobenzene,
1-chloro-2,4-diisocyanatobenzene, tris-(4-isocyanatophenyl)methane,
naphthalene diisocyanates, fluorene diisocyanates, 4,4'-biphenyl
diisocyanate; phenylene diisocyanates, 3,3'-dimethyl-4,4'-biphenyl
diisocyanate, p-isocyanatobenzyl isocyanate,
tetrachloro-1,3-phenylene diisocyanate, and related isocyanates,
2,4,6-tribromo-1,3-phenylene diisocyanate,
bis(2-isocyanatoethyl)benzene, vinyl polymers containing
isocyanatoethyl methacrylate as a monomer or comonomer, prepolymers
of polyisocyanates with polyhydroxyl or polyamino compounds, such
as prepolymers of
3-isocyanatomethyl-3,3,5-trimethylcyclohexylisocyanate, tolylene
diisocyanate, menthane diisocyanate,
4,4'-methylene-bis(cyclohexylisocyanate), 2-isocyanatoethyl
6-isocyanatocaproate, 2-isocyanatoethyl 2-isocyanatopropionate and
the like, with polyether polyols, polyester polyols, and the like.
Preferred isocyanates of this invention include
N,N'N"-tris-(6-isocyanatohexamethylene)biuret;
4,4'-methylene-bis(cyclohexylisocyanate), and aliphatic
diisocyanate derived from a 36 carbon diamine,
methylene-bis(4-phenylisocyanate); toluene diisocyanate,
3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 2
-isocyanatoethyl-6-isocyanatocaproate or
2-isocyanatoethyl-2-isocyanatopropionate.
The preparation of the isocyanate prepolymers useful in the
compositions of this invention is well-known in the art. The
preparation of these prepolymers involves the reaction of the
hydroxy terminated polyester, with a diisocyanate or
polyisocyanate, using an excess of the isocyanate to yield an
isocyanate terminated prepolymer product. A description of the
techniques for preparing the isocyanate prepolymers is found in J.
H. Saunders and K. C. Frisch, Polyurethanes: Chemistry and
Technology, Part II, Interscience (New York, 1964); especially on
pages 8 to 49.
Other polyfunctional isocyanates useful in the compositions of the
invention are disclosed in U.S. Pat. Nos. 3,162,664; 3,427,346;
3,275,679; 3,352,830; 2,729,666; 2,768,154; 3,267,122; 3,281,378;
3,124,605 and 2,718,516.
A preferred embodiment of this invention is a hydrocurable coating
composition comprising a
hydroxy(polypentylenecarbonyloxy)ethyloxazolidine of the following
formula: ##STR2## wherein R.sup.4 is hydrogen or lower alkyl, such
as methyl, ethyl, n-propyl, isopropyl, n-butyl and the like; z' is
an integer of 5-20 and an isocyanate selected from
N,N',N"-tris(6-isocyanatohexamethylene)biuret:
4,4'-methylene-bis-(cyclohexylisocyanate); a diisocyanate derived
from a 36 carbon diamine (DDI), methylene-bis-(4-phenylisocyanate),
toluene diisocyanate or isophorone diisocyanate. These compounds
afford high solids containing compositions having an outstanding
speed of cure and exceptional pot life.
The reaction of the hydroxy(polyalkylenecarbonyloxy)
alkyleneoxazolidine (I, supra) with a diisocyanate can afford two
products depending on the molar ratio of diisocyanate employed. To
afford a monooxazolidine isocyanate polymer the molar ratio of the
isocyanate functionality must be equal to or greater than one (1).
Preferably the molar ratio of isocyanate functionality is in the
range of from about 1 to about 3. The following equation
illustrates this reaction. ##STR3## wherein R.sup.1, R.sup.2 and
R.sup.3, X, Y and z are as defined above. m is an integer equal to
the valence of Z and Z is a polyvalent organic isocyanate reside
derived from a known isocyanate. The polymer (III, supra), is a
hydrocurable polymer.
When the molar ratio of a polyisocyanate (II, infra) is reduced to
0.5 or less, a chain extended, coupled bisoxazolidine (IV, infra)
can be prepared which is an isocyanate prepolymer. The following
formula illustrates this product: ##STR4## wherein R.sup.1,
R.sup.2, R.sup.3, X, Y, Z, n, m and z are as defined above. Polymer
IV (supra) is a stable polyester urethane which can be further
blended with additional di- or polyisocyanates to form hydrocurable
compositions.
The hydroxy(polyalkylenecarbonyloxy)alkyleneoxazolidine (I, supra)
is prepared by treating a hydroxyalkyleneoxazolidine (V, supra)
with a lactone (VI, infra) having at least five (5) carbon atoms in
the presence of a transesterification catalyst at a temperature in
the range of from about 0.degree. to 200.degree. C. for a period of
time from about 1 to about 24 hours. The following equation
illustrates this process: ##STR5## wherein R.sup.1, R.sup.2,
R.sup.3, X, Y and n are as defined above. By employing a large
molar excess of the lactone (VI), for example, at least 5 moles of
lactone per mole of the hydroxyalkyleneoxazolidine (V), there is
assured a complete reaction of the hydroxyalkyleneoxazolidine
(V).
Catalysts which may be employed include the organometallic
compounds, metals, metal hydrides, metal alkoxides, amines and the
like. The preferred catalysts are metal alkoxides such as sodium
methoxide and the like, tetrapropyl titanate, tetraalkylammonium
alkoxides, such as tetraethylammonium ethoxide, and the like and
alkyl tin oxides, esters and alkoxides such as dibutyltin oxide,
dibutyltin dimethoxide, dibutyltin diacetate or dilaurate and the
like.
The preparation of the hydroxyalkyleneoxazolidines (V, supra) is
disclosed in U.S. Pat. No. 3,743,626 which patent is hereby
incorporated by reference.
Examples of the lactones which may be employed include, for
example, .beta.-propiolactone, .delta.-valerolactone,
.epsilon.-caprolactone, 7-hydroxyheptanoic acid lactone,
8-hydroxyoctanoic acid lactone, 12-hydroxydodecanoic acid lactone,
13-hydroxytridecanoic acid lactone, 14-hydroxytetradecanoic acid
lactone, 15-hydroxypentadecanoic acid lactone,
16-hydroxyhexadecanoic acid lactone, 17-hydroxyheptadecanoic acid
lactone; the .alpha., .alpha.-dialkyl-.beta.-propiolactones, for
example, .alpha.,.alpha.-dimethyl-.beta.-propiolactone,
.alpha.,.alpha.-diethyl-.beta.-propiolactone,
.alpha.,.alpha.-dipropyl-.beta.-propiolactone and the like;
.delta.-valerolactones, wherein the alkyl is from 1-12 carbon
atoms, such as isopropyl, butyl, hexyl, decyl, dodecyl and the
like; dialkyl-.delta.-valerolactones in which the alkyl groups of
from 1-12 carbon atoms are substituted on the same or different
carbon atoms in the cyclic ring; the monoalkyl-, dialkyl-or
trialkyl-.epsilon.-caprolactones, wherein alkyl is from 1-12 carbon
atoms, the monoalkoxy- and dialkoxy-.delta.-valerolactones and
.epsilon.-caprolactones, for example, the monomethoxy-,
mono-ethoxy-, monoisopropoxy-, dimethoxy-, diethoxy and
dibutoxy-.delta.-valerolactones, .epsilon.-caprolactones and the
like. Further illustrative cyclic esters include
3-ethyl-2-keto-1,4-dioxane,
.gamma.-(1-isopropyl-4-methylcyclohexyl)-.epsilon.-caprolactone,
3-bromo-2,3,4,4-tetrahydrobenzoxepin-2-one,
2-(2'-hydroxyphenyl)-benzene carboxylic acid lactone,
10-hydroxyundecanoic acid lactone,
2,5,6,7-tetrahydrobenzoxepin-2-one,
9-oxabicyclo[5,2,2]undecan-8-one, 4-oxa-14-hydroxytetradecanoic
acid lactone, .alpha.,.alpha.-bis(chloromethyl)-propiolactone,
1,4-dioxane-2-one, 3-n-propyl-2-keto-1,4-dioxane,
3-(2-ethylhexyl)-2-keto-1,4-dioxane, and the like. Illustrative
subclasses of cyclic esters which are suitable in the process of
the instant invention include the unsubstituted lactones and
oxalactones which contain from 6 to 18 atoms in the lactone ring,
preferably .delta.-valerolactone, .epsilon.-caprolactone,
ketodioxanes and the like; the mono- and polyalkyl substituted
lactones and oxalactones which contain from 6 to 8 atoms in the
lactone ring, preferably, the mono- and poly lower alkyl
.epsilon.-valerolactones, .epsilon.-caprolactones, and their
corresponding oxalactones wherein the alkyls contain from 1 to 4
carbon atoms; mono- and polyalkoxy substituted lactones and
oxalactones which contain from 6 to 8 atoms in the lactone ring,
preferably the mono- and poly-lower alkoxy-.delta.-valerolactones,
.epsilon.-caprolactones, and their corresponding oxalactones
wherein the alkoxy contains from 1 to 4 carbon atoms.
The unsubstituted and substituted .delta.-valerolactones,
.delta.-caprolactones L-enantholactones, and higher membered
lactones, for example, mono- and polyalkyl substituted
.delta.-valerolactones, mono- and polyalkoxy substituted
.delta.-valerolactones, mono- and polycycloalkyl substituted
.delta.-valerolactones, aryl substituted .delta.-valerolactones,
mono- and polyhaloalkyl substituted .delta.-valerolactones, mono-
and polyalkyl substituted .epsilon.-caprolactones, mono- and
polyalkoxy .epsilon.-caprolactones, aryl substituted
.epsilon.-caprolactones, mono- and polyhaloalkyl substituted
.epsilon.-caprolactones, mono- and polyalkyl substituted
L-enantholactones, and various other lactones described previously
can be prepared by reacting the corresponding cyclic ketone with an
anhydrous solution comprising peracetic acid and acetone. It is
desirable to add the peracetic acid solution to an excess of the
ketone, for example, a 5 to 1 molar ratio of ketone to peracetic
acid, in a still kettle maintained under reflux. The pressure can
be adjusted so as to provide a kettle temperature of about
70.degree. C. Acetone, acetic acid by-product and minor amounts of
ketone can be continuously removed throughout the addition period.
Subsequently, the lactone product can be recovered from the still
kettle by conventional techniques such as by distillation.
The reaction between the oxazolidines (I, supra) and the isocyanate
component is initiated by water, for example, atmospheric moisture.
A trace amount of atmospheric moisture is generally sufficient to
initiate the polymerization reaction and cure the composition. If
desired, water, for example, other than atmospheric, may be added
to the compositions to effect cure, but this is not necessary. It
is believed that the polymeric materials formed from the
compositions of the invention result from the rapid hydrolysis of
the oxazolidine which opens the oxazolidine ring at one of the
bonds to the oxygen atom. The following reaction sequence
illustrates the postulated path of the hydrolysis: ##STR6##
The amino alcohol produced has active hydrogen sites which react
rapidly with an isocyanate. The isocyanate can react with either
the amino group or the hydroxy group but is believed to be faster
with the amino group.
Since the isocyanate is polyfunctional and the oxazolidine reacts
in the presence of water as a polyfunctional compound, their
reaction, as described above, will produce a highly polymeric
material. Of course, a compound having more than one oxazolidine
group will react as a polyfunctional material even if the
isocyanate and oxazolidine are present in such proportions as to
cause primary reaction during cure with the amine functionality
only. While the hydrocuring reaction, that is, the hydrolysis and
ensuing polymerization, will normally occur rapidly at ambient
temperatures, elevated temperatures may facilitate reaction and
curing under some conditions.
The hydrocuring reaction can be carried out with or without a
catalyst. Under certain conditions, an acid catalyst, such as
p-toluenesulfonic acid, dibutyltin octoate, zinc chloride, hydrogen
chloride and the like, may be advantageously employed. The acid
catalyst will generally be present in an amount of from about
0.001% to about 10% by weight based on the weight of oxazolidine,
and preferably from about 1% to about 5% by weight.
The compositions of the invention need not contain a solvent, but
an inert or relatively inert solvent can be added to the
composition, if desired, either at the time of original formulation
or at the time of use. The rate of the hydrolysis of the
oxazolidine and the subsequent reaction with isocyanate can be
influenced by the presence of a solvent. Solvents which are
suitable for use in the compositions of the invention should be
substantially free from active hydrogen atoms as determined by the
Zerewitinoff method, described in Kohler et al., J. Am. Chem. Soc.,
40, 2181-8 (1927), and should also be substantially anhydrous.
Included among the solvents which can be used are toluene, xylene,
liquid aliphatic hydrocarbons, isopropyl ether, ethyl acetate,
.beta.-ethoxyethyl acetate, methyl ethyl ketone and the like, as
well as mixtures of such solvents. Pigments, dyes, fillers,
antioxidants, antiozodants, stabilizers, flow control agents or
other optional ingredients can also be included in the compositions
of the invention.
The compositions of the invention can be used in forming films,
fibers, paints, lacquers, varnishes, seamless flooring, caulks, as
coatings, impregnants, adhesives for both natural and synthetic
substrates, such as paper, textiles, wood, plastics, metal or
leather and also as binders for non-woven fabrics. To prepare
coatings and films, the compositions of the invention can be
applied with or without solvent by casting permanently or removably
onto a suitable substrate such as wood, metal, plastic, paper or
leather.
The compositions of the invention provide an improved combination
of increased pot life and increased curing speed with respect to
those combinations which contain compounds having free amine
groups.
Various embodiments of the compositions of the invention and the
polymeric materials formed from them exhibit a number of desirable
and advantageous properties. Some of the compositions can be sealed
in a single package so that if moisture is excluded, undesirable
thickening or gelling do not occur during storage. Even those
compositions that are not extremely stable in one-pot formulations
offer improved stability over conventional two-pot urethane
systems. Since exposure to atmospheric mositure will effect cure,
no additional materials need be mixed with these compositions at
the time of use, thus facilitating greatly their handling.
Furthermore, when no solvent is incorporated in the compositions,
they are extremely high solids coating materials. When some of the
compositions are used for the impregnation of leather, they provide
significant improvements in break over known urethane systems.
The examples which follow illustrate the hydroxy
(polyalkylenecarbonyloxy)alkyleneoxazolidines (I) of the invention
and the methods by which they are prepared. However, the examples
are illustrative only and it will be apparent to those having
ordinary skill in the art that all of the products embraced by
Formula I, supra, may also be prepared in an analgous manner by
substituting the appropriate starting materials for those set forth
in the examples.
EXAMPLE 1
3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1240)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is charged hydroxyethyloxazolidine
(HEOX, 1.5 mole, 175.5 g.), .epsilon.-caprolactone (3.0 mole, 342.0
g.) and dibutyltin oxide (Bu.sub.2 SnO, 0.75% on polyester, 7.73
g.). The flask charge is heated to 100.degree. C. and held at that
temperature while .epsilon.-Cl (4.5 mole, 513.0 g.) is added over a
60 minute period. After the addition is complete, the batch is held
at 100.degree. C. for 4 hours to complete reaction. The product
3-[hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine (MW 1240) is
a fluid while hot but on cooling forms a waxy solid (acid 0.130
meg./g., amine 1.38 meq./g., GPC mol. wts. M.sub.w 1240, M.sub.n
770 M.sub.w /M.sub.n 1.62, calcd. mol. wt. 687, equivalent weight
for reaction with isocyanate 229 g./eq.
EXAMPLE 2
Hydrocurable composition of
3-[hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine (MW 1240)
and DDI
3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1240)
(0.01 eq.,2.29 g.) is dissolved in xylene (5.3 g.) and a
diisocyanate derived from a 36 carbon diamine (DDI) (.01 eq.,3.00
g.) is added. After mixing, a 10 mil wet film is cast on a glass
plate and is allowed to cure at room temperature (tack-free time 60
minutes, clear film, swelling by 2-ethoxyethyl acetate is light,
pencil hardness <6B).
EXAMPLE 3
Hydrocurable composition of
3-[hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine and
N,N',N"-tris(6-isocyanatohexamethylene)biuret
3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine mol. wt. 1240
(0.01 eq., 2.29 g., is dissolved in xylene (3.6 g.) and
N,N',N"-tris(6-isocyanatohexamethylene)biuret (0.01 eq., 2.50 g.)
is added. After mixing, a 10 mil wet film is cast on a glass plate
and allowed to cure at room temperature (tack-free time 10 minutes,
clear film, swelling by 2-ethoxyethyl acetate is very slight,
pencil hardness H).
EXAMPLE 4
Hydrocurable Composition of
3-[Hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine and
4,4'-methylene-bis(cyclohexylisocyanate)
3-[(Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (0.01 eq.,
2.29 g.) is dissolved in xylene (3.6 g.) and
4,4'-methylenebis(cyclohexylisocyanate) (0.01 eq., 1.31 g.) is
added. After mixing, a 10 mil. wet film is cast on a glass plate
and allowed to cure at room temperature (tack-free time 60 minutes,
clear film, swelling by 2-ethoxyethyl acetate is very slight,
pencil hardness F).
EXAMPLE 5
Composition of
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine and
4,4'-methylenebis(cyclohexylisocyanate
A mixture of 3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine
(0.64 mole, 443.0 g.) is heated to 80.degree. C. and then
4,4'-methylenebis(cyclohexylisocyanate) (0.32 mole, 83.8 g.) is
added. The mixture exotherms to 113.degree. C. and is allowed to
cool with stirring to 100.degree. C. over a 30 minute period. At
room temperature this isocyanate coupled bisoxazolidine product
forms a waxy solid (calcd. mol. wt. 1636, 409 g./eq. for reaction
with isocyanate). The product is mixed with xylene and various di-
and polyisocyanates to produce moisture curing coatings.
EXAMPLE 6
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine and DDI
A mixture of 3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine
(1.50 mole, 1030.5 g.) is heated to 80.degree. C. and DDI (0.75
mole, 450 g.) is added. The mixture exotherms to 98.degree. C. and
is allowed to cool with stirring to 80.degree. C. over 30 minutes.
At room temperature this isocyanate coupled bisoxazolidine product
forms a waxy solid (calcd. mol. wt. 1976, 494 g./eq. for reaction
with isocyanates).
EXAMPLE 7
Hydrocurable Composition of the bisoxazolidine of Example 6 and
N,N',N"-tris(6-isocyanatohexamethylene)biuret
The product of Example 6 (0.01 eq., 4.94 g.) is dissolved in xylene
(7.5 g.) and N,N',N"-tris(6-isocyanatohexamethylene)biuret (0.01
eq., 2.50 g.) is added. After mixing, a 10 mil wet film is cast on
a glass plate and allowed to cure at room temperature (tack-free
time 15 minutes, clear film, swelling in 2-ethoxyethyl acetate
light).
EXAMPLE 8
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1590)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is added HEOX (0.4 mole, 46.8 g.),
.epsilon.-caprolactone (3.2 mole, 364.8 g.) and Bu.sub.2 SnO (1.0%
on polyester, 4.14 g.). The mixture is heated to 100.degree. C. and
held there for 260 minutes while .epsilon.-caprolactone reacts. The
product is a fluid while hot but on cooling forms a waxy solid
(acid 0.091 meq./g., amine 0.936 meq./g., GPC mol. wt. M.sub.w
1590, M.sub.n 980, M.sub.w /M.sub.n = 1.62, calcd. mol. wt. 1030,
equivalent weight for reaction with isocyanate 343 g./3 g.).
EXAMPLE 9
Hydrocurable Composition of
3-[Hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine (MW 1590)
and DDI
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1590)
(0.01 eq. 3.43 g.) is dissolved in xylene (6.4 g.) and DDI (0.01
eq. 3.00 g.) is added. After mixing, a 10 mil film is cast on a
glass plate and is allowed to cure at room temperature (tack-free
time 60 minutes, hazy film, swelling by 2-ethoxyethyl acetate is
light, pencil hardness <6B.
EXAMPLE 10
Hydrocurable Composition of
3-[Hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine (MW 1590)
and N,N',N"-tris(6-isocyanatohexamethylene)biuret
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1590)
(0.01 eq. 3.43 g.) is dissolved in xylene (5.0 g.) and
N,N',N"-tris(6-isocyanatohexamethylene)biuret (0.01 eq. 2.50 g.) is
added. After mixing, a 10 mil wet film is cast on a glass plate and
allowed to cure at room temperature (tack-free time 10 minutes,
clear film, swelling by 2-ethoxyethyl acetate very slight, pencil
hardness F).
EXAMPLE 11
Hydrocurable Composition of
3-[Hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine (MW 1590)
N,N',N"-tris(6-isocyanatohexamethylene)biuret
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1590)
(0.01 eq. 3.43 g.) is dissolved in xylene (4.7 g.) and
4,4'-methylenebis(cyclohexylisocyanate) (0.01 eq.; 1.31 g.) is
added. After mixing, a 10 mil wet film is cast on a glass plate and
allowed to cure at room temperature (tack-free time 120 minutes,
clear film, swelling by 2-ethoxyethyl acetate very slight, pencil
hardness 3B).
EXAMPLE 12
Hydrocurable Composition of
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1590) and
toluene diisocyanate
3-Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1590)
(0.01 eq. 3.43 g.) is dissolved in xylene (4.4 g.) and toluene
diisocyanate (0.01 eq. 0.9 g.) is added. After mixing, a 10 mil wet
film is cast on a glass plate and allowed to cure at room
temperature (tack-free time 60 minutes, clear film, swelling by
2-ethoxyethyl acetate slight).
EXAMPLE 13
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 1257)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is charged HEOX (0.09 mole, 105.3 g.)
.epsilon.-caprolactone (1.8 mole, 205.2 g.) and Bu.sub.2 SnO (0.75%
on polyester, 8.49 g.). The flask is heated to 100.degree. C. and
held at that temperature while more .epsilon.-caprolactone (7.2
mole, 820.8 g.) is added over 60 minutes. The batch is held at
100.degree. C. for 6 hours to complete reaction. The product
hydroxy-(polypentylenecarbonyloxy)ethyloxazolidine is a fluid while
hot but on cooling, forms a waxy solid (calcd. mol. wt. 1257,
equivalent weight for reaction with isocyanate, 419 g./eq.
EXAMPLE 14
Bisoxazolidine of
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine and
4,4'-methylenebis(cyclohexylisocyanate)
The bisoxazolidine of
3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine 0.42 mole
531.9 g.) is heated to 80.degree. C.
4,4'-methylenebis(cyclohexylisocyanate) (0.21 moles, 55.0 g.) is
then added. The mixture exotherms to 101.degree. C. and is held for
30 minutes to complete the reaction. At room temperature the
product is a waxy solid (calcd. mol. wt. 2776, 694 g./eq. for
reaction with isocyanates).
EXAMPLE 15
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (MW 2570)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is added HEOX (0.60 mole, 70.2 g.)
.epsilon.-caprolactone (1.2 mole, 136.8 g.) and Bu.sub.2 SnO (0.75%
of total polyester, 8.22 g.). The flask charge is heated to
100.degree. C and held at that temperature while more
.epsilon.-caprolactone (7.8 mole, 889.2 g.) is added over a 60
minute period. After the addition is complete, the batch is
maintained at 100.degree. C. for 6 hours to complete reaction. The
product is a fluid while hot but on cooling forms a waxy solid
(acid 0.09 meq./g., amine 0.523 meq./g., GPC mol. wts. Mw 2570 Mn
1690 M.sub.w /M.sub.n 52; calcd. mol. wt. 1827. Equivalence for
reaction with isocyanate 609 g./eq.
EXAMPLE 16
Hydrocurable Composition of
3-[Hydroxy(polypentylene-carbonyloxy)ethyl]oxazolidine and DDI
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (0.01 eq.
6.09 g.) is dissolved in xylene (9.0 g.) and DDI (0.01 eq. 3.00 g.)
is added. After mixing, a 10 mil wet film is cast on a glass plate
and is allowed to cure at room temperature (tack-free time 90
minutes, hazy film, swelling in 2-ethoxyethyl acetate is moderate
with some lifting from glass, pencil hardness <6B).
EXAMPLE 17
Hydrocurable Composition of
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine and
N,N',N"-bis(6-isocyanatohexamethylene)biuret
Bisoxazolidine of
3-[hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (0.01 eq.
6.09 g.) is dissolved in xylene (8.6 g.) and
N,N',N"-bis(6-isocyanatohexamethylene)biuret (0.01 eq. 2.50 g.) is
added. After mixing, a 10 mil wet film is cast on a glass plate and
allowed to cure at room temperature (tack-free time 15 minutes,
clear film, swelling in 2-ethoxyethyl acetate is very slight,
pencil hardness <6B).
EXAMPLE 18
Hydrocurable Composition of
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine and toluene
diisocyanate
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]oxazolidine (0.01 eq.
6.09 g.) is dissolved in xylene (7.0 g.) and toluene diisocyanate
(0.01 eq. 0.9 g.) is added. After mixing, a 10 mil wet film is cast
on a glass plate and is allowed to cure at room temperature
(tack-free time 60 minutes, hazy film, swelling in 2-ethoxyethyl
acetate slight).
EXAMPLE 19
Hydroxy(polypentylenecarbonyloxy)ethyloxazolidine and
4,4'-methylenebis(cyclohexylisocyanate)
Hydroxy(polypentylenecarbonyloxy)ethyloxazolidine 0.28 mole, 515.4
g.) is heated to 80.degree. C. and
4,4'-methylenebis-(cyclohexylisocyanate) (0.14 mole, 36.7 g.) is
added. The mixture exotherms to 92.degree. C. and is held at
95.degree.-100.degree. C. for 30 minutes to complete reaction. At
room temperature, this isocyanate coupled, bisoxazolidine product
forms a waxy solid (calcd. mol. wt. 3916, 979/eq. for reaction with
isocyanate). The product is mixed with xylene and various di- and
polyisocyanates to produce moisture curing coatings.
EXAMPLE 20
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(MW-730)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is added
2-isopropyl-1-hydroxyethyloxazolidine (IPOX, as an 82.3% solution
in xylene, 1.50 mole, 289.8 g.) and Bu.sub.2 SnO (0.25% on total
polyester 2.73 g). The flask is heated to 125.degree. C. and
.epsilon.-caprolactone (7.5 mole, 855.0 g.) is added over a 60
minute period. When the addition is complete, the batch is held at
125.degree. C. for 2 hours to complete the reaction. The product,
3-[hydroxy(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) is a fluid while hot but on cooling to room temperature
forms a waxy solid (calcd. mol. wt. 730, solids 95.2%, equivalent
weight as supplied for reaction with isocyanate, 255 g./eq.
EXAMPLE 21
Hydrocurable Composition of
3-[Hydroxy(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
and N,N',N"-bis(6-isocyanatohexamethylene)biuret
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(0.01 eq., 2.55 g.) is dissolved in xylene (5.1 g.) and
N,N',N"-bis(6-isocyanatohexamethylene)biuret (0.01 eq., 2.50 g.) is
added. After mixing, a 10 mil wet film is cast on a glass plate and
allowed to cure at room temperature (tack-free time 60 minutes,
clear film, swelling by 2-ethoxyethyl acetate very slight, pencil
hardness F).
EXAMPLE 22
Hydrocurable Composition of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) and 4,4'-methylenebis(cyclohexylisocyanate)
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) (0.01 eq., 2.55 g.) is dissolved in xylene (3.9 g.) and
4,4'-methylenebis(cyclohexylisocyanate) (0.01 eq., 1.31 g.) is
added. After mixing, a 10 mil wet film is cast on a glass plate and
allowed to cure at room temperature (tack-free time 120 minutes,
clear film, swelling with 2-ethoxyethyl acetate slight, pencil
hardness F).
EXAMPLE 23
Bisoxazolidine
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) and 4,4'-methylenebis(cyclohexylisocyanate)
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) (0.716 mole, 547.5 g.) is heated to 100.degree. C. and
then 4,4'-methylenebis(cyclohexylisocyanate) (0.358 mole, 93.8 g.)
is added. The mixture exotherms to 127.degree. C. and is allowed to
cool, with stirring, to 100.degree. C. for 30 minutes. At room
temperature, this isocyanate coupled, bisoxazolidine product is a
waxy solid (calcd. mol. wt. 1720 solids, 96.0% eq./wt. as supplied
for reaction with isocyanates 448 g./eq.). The product is mixed
with xylene and various di- and polyisocyanates to produce moisture
curing coatings and adhesives.
EXAMPLE 24
Bisoxazolidine of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) and N,N',N"-bis(6-isocyanatohexamethylene)biuret
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) (0.75 mole, 573.8 g.) is heated to 80.degree. C. and then
N,N',N"-bis(6-isocyanatohexamethylene)biuret (0.25 mole, 188.0 g.)
is added. The mixture exotherms to 103.degree. C. and is held at
100.degree. C. with stirring for 30 minutes. At room temperature,
this isocyanate coupled, bisoxazolidine polyester slowly forms a
waxy solid (calcd. mol. wt. 1834, solids 90.3%, equivalent weight
as supplied for reaction with isocyanate 508 g./eq.). The product
is mixed with xylene and various di- and polyisocyanates to produce
moisture curing coatings.
EXAMPLE 25
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1072)
To a flask equipped for stirring, addition, heating, reflux, and
automatic temperature control is added IPOX (0.40 mole, 78.1 g.),
.epsilon.-caprolactone (3.2 mole, 364.8 g.) and Bu.sub.2 SnO (1% on
polyester, 4.14 g.). The mixture is heated to 100.degree. C. and
held there for 8 hours. The product is a fluid while hot but on
cooling forms a waxy solid (calcd. mol. wt. 1072, solids 96.7%,
equivalent weight as supplied for reaction with isocyanates 369
g./eq.).
EXAMPLE 26
Hydrocurable Composition of
3-[Hydroxy-(polypentylenecarbonyloxy)-2-isopropylethyloxazolidine
and DDI
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(0.01 eq., 3.69 g.) is dissolved in xylene (6.7 g.) and DDI (0.01
eq., 3.00 g.) is added. After mixing, a 10 mil wet film is cast on
a glass plate and is allowed to cure at room temperature (tack-free
time 240 minutes, clear film, swelling by 2-ethoxyethyl acetate
moderate, pencil hardness < 6B).
EXAMPLE 27
Hydrocurable Composition of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1072) and N,N',N"-tris(6-isocyanatohexamethylene)-biuret
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1072) (0.01 eq., 3.69 g.) is dissolved in xylene (6.2 g.) and
N,N',N"-tris(6-isocyanatohexamethylene) biuret (0.01 eq., 2.50 g.)
is added. After mixing, a 10 mil wet film is cast on a glass plate
and allowed to cure at room temperature (tack-free time 30 minutes,
clear film, swelling by 2-ethoxyethyl acetate very slight, pencil
hardness F).
EXAMPLE 28
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1072) and 4,4'-methylenebis-(cyclohexylisocyanate)
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1072) (0.01 eq., 3.69 g.) is dissolved in xylene (5.0 g.) and
4,4'-methylenebis(cyclohexylisocyanate) (0.01 eq., 1.31 g.) is
added. After mixing, a 10 mil wet film is cast on a glass plate and
allowed to cure at room temperature (tack-free time 120 minutes,
clear film, swelling with 2-ethoxyethyl acetate slight, pencil
hardness F).
EXAMPLE 29
Hydrocurable Composition of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropylethyloxazolidine
(Mw 1072) and toluene diisocyanate
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1072) (0.01 eq., 3.69 g.) is dissolved in xylene (4.6 g.) and
toluene diisocyanate (0.01 eq., 0.9 g.) is added. After mixing, a
10 mil wet film is cast on a glass plate and allowed to cure at
room temperature (tack-free time 30 minutes, clear film, swelling
with 2-ethoxyethyl acetate slight).
EXAMPLE 30
Bisoxazolidine of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1300)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is added IPOX (0.8 mole, 154.6 g.)
and Bu.sub.2 SnO (0.25%) on polyester, (26.0 g.). The flask is
heated to 125.degree. C. and .epsilon.-caprolactone (8.0 mole, 9.12
g.) is added over a 60 minute period. When the addition is
complete, the batch is held at 125.degree. C. for 10 more minutes
to ensure a complete reaction. The product is a waxy solid (calcd.
mol. wt. 1300, solids 97.2%, equivalent weight as supplied for
reaction with isocyanate, 445 g./.eq.). The product is mixed with
xylene and various di- and polyisocyanates to produce moisture
curing coatings.
EXAMPLE 31
Bisoxazolidine of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 730) and 4,4'-methylenebis(cyclohexylisocyanate)
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw-730) (0.374 moles, 499.2 g.) is heated to 98.degree. C. and
then 4,4'-methylenebis(cyclohexylisocyanate) (0.187 mole, 49.0 g.)
is added. The mixture exotherms to 117.degree. C. and is allowed to
cool with stirring to 100.degree. C. over 30 minutes. At room
temperature this isocyanate coupled, bisoxazolidine product is a
waxy solid (calcd. mol. wt. 2860, solids 97.5% eq. wt. as supplied
for reaction with isocyanates 733 g./eq.). The product is mixed
with xylene and various di- and polyisocyanates to produce moisture
curing coatings.
EXAMPLE 32
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1860)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is added IPOX (0.578 mole, 112.8 g.)
and Bu.sub.2 SnO (0.2% on polyester, 2.75 G). The flask is heated
to 125.degree. C. and .epsilon.-caprolactone (8.67 mole, 988.4 g.)
is added over a 90 minute period. When the feed is complete the
batch is held at 125.degree. C. for 60 minutes to complete the
reaction. The product is solid (calcd. mol. wt. 1860, solids 98.1%,
equivalent weight as supplied for reaction with isocyanates 635
g./eq.).
EXAMPLE 33
Bisoxazolidine of
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1860) and 4,4'-methylenebis(cyclohexylisocyanate)
3-[Hydroxy-(polypentylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 1860) (0.28 mole, 534.0 g.) is heated to 100.degree. C. and
then 4,4-methylenebis(cyclohexylisocyanate) (0.14 mole, 36.7 g.) is
added. The mixture exotherms to 112.degree. C. and is allowed to
cool with stirring to 100.degree. C. for 30 minutes. At room
temperature this isocyanate coupled, bisoxazolidine product is a
waxy solid (calcd. mol. wt. 4000, solids 98.2% eq. wt. 1018
g./eq.). The product is mixed with xylene and various di- and
polyisocyanates to produce moisture curing coatings.
EXAMPLE 34
3-[Hydroxy-(polybutylenecarbonyloxy)ethyl]-2-isopropyloxazolidine
(Mw 3945)
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is added IPOX (0.20 mole, 39.6 g.)
and Bu.sub.2 SnO (0.25% on polyester, 0.92 g.). The flask is heated
to 125.degree. C. and a solution of .epsilon.-caprolactone (2.6
mole, 296.4 g.) and valerolactone (0.4 mole, 40.0 g.) is added over
a 60 minute period. When the feed is complete, the batch is held at
125.degree. C. for 90 minutes to complete reaction. The flask is
cooled to 100.degree. C. and then
4,4'-methylenebis(cyclohexylisocyanate) (0.10 mole, 26.2 g.) is
added. The reaction exotherms to 113.degree. C. and is allowed to
cool with stirring to 100.degree. C. for 30 minutes. At room
temperature this isocyanate coupled, bisoxazolidine product is a
waxy solid (calcd. mol. wt. 3945, solids 98.3% equ. wt. as supplied
for reaction with isocyanates 1005 g./eq.). The product is mixed
with xylene and various di- and polyisocyanates to produce moisture
curing coatings.
EXAMPLE 35
Hydrocurable Composition of
3-[Hydroxy(polypentylenecarbonyloxy)propyl]tetrahydro-1,3-oxazine
and N,N',N"-tris-(6-isocyanatohexamethylene)biuret
Step A
3-(.beta.-hydroxypropyl)tetrahydro-1,3-oxazine
To a glass reaction vessel equipped with stirrer, thermometer, and
condenser fitted with a water trap is added di-(3-hydroxypropyl)
amine (3.0 mole, 399 g.) and toluene (500 g.). Paraformaldehyde
(3.15 mole, 90% pure, 105 g.) is weighed out and about 1/3 is added
to the amine solution. The resulting mixture is stirred and heated
to 90.degree. C. while slowly adding the remaining paraformaldehyde
in about 70 minutes. The reaction is heated to reflux and the water
separated. After 4 hours, a total of 63 ml. of water is removed.
Toluene is removed at reduced pressure. The residue is distilled at
high vacuum to yield
3-(.beta.-hydroxypropyl)tetrahydro-1,3-oxazine.
Step B
Hydrocurable composition of
3-[hydroxy(polypentylenecarbonyloxy)propyl]tetrahydro-1,3-oxazine
and N,N'-N"-tris-(6-isocyanatohexamethylene)biuret
To a flask equipped for stirring, addition, heating, reflux and
automatic temperature control is charged
3-(hdroxypropyl)tetrahydro-1,3-oxazine (0.9 mole, 130.5 g.),
.epsilon.-caprolactone (1.8 mole, 205.2 g.) and Bu.sub.2 SnO (0.75%
on polyester, 8.6 g.). The flask is heated to 100.degree. C. and
held at that temperature while .epsilon.-caprolactone (7.2 mole,
820.8 g.) is added over a 60 minute period. After the feed is
complete the batch is held at 100.degree. C. for 6 hours to
complete the reaction. The product
3-[hydroxy(polypentylenecarbonyloxy)propyl]tetrahydro-1,3-oxazine
is a fluid while hot but on cooling forms a waxy solid (calcd. mol.
wt. 1285, equivalent weight for reaction with isocyanate, 426
g./eq.). The product (0.5 mole) is mixed with xylene and to produce
a moisture curing coating.
EXAMPLE 36
Bisoxazine of
3-[Hydroxy(polypentylenecarbonyloxy)propyl]tetrahydro-1,3-oxazine
3-[Hydroxy(polypentylenecarbonyloxy)propyl]tetrahydro-1,3-oxazine
(0.42 mole, 539.7 g.) is melted and heated to 80.degree. C. and
4,4'-methylenebis(cyclohexylisocyanate) (0.21 mole, 55.0 g.) is
added. The mixture exotherms to 101.degree. C. and is held at
100.degree. C. for 30 minutes to complete the reaction. At room
temperature this isocyanate coupled, bis(tetrahydro-1,3-oxazine) is
a waxy solid (calcd. mol. wt. 2832, 708 g./eq. for reaction with
isocyanate). The product is mixed with various di- and
polyisocyanates to produce moisture curing coatings.
By treating a 2-(R.sup.2) hydroxyethyloxazolidine (1 mole) with
.epsilon.-caprolactone ("A" moles) in the presence of a catalyst a
correspondingly substituted
2-(R.sup.2)hydroxy(polypentylenecarbonyloxy)ethyloxazolidine is
obtained which product when reacted with one or more equivalents of
an isocyanate affords the correspondingly substituted hydrocurable
composition. Table I, below, illustrates the R.sup.2 substituent,
the number of moles of .epsilon.-caprolactone ("A"), the amount and
type of catalyst, the temperature, the reaction time, and the
isocyanate employed. Also, the molecular weight and equivalent
weight of the hydrocurable composition, when obtained, are
reported.
The following is an explanation of the isocyanates represented by
Roman numerals and of other various symbols employed in the
tables.
1. I' is diisocyanate having a 36 carbon diamine (DDI)
2. ii' is 4,4'-methylenebis(cyclohexylisocyanate)
3. III' is methylene-bis(4-phenylisocyanate)
4. IV' is toluene diisocyanate
5. V' is 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate
6. VI' is N,N',-bis(6-isocyanathohexamethylene)biuret
7. HEOX is N-hydroxyethyloxazolidine
8. IPOX is 2-isopropyl-N-hydroxyethyloxazolidine
9. OX indicates an oxazolidine
10. IC indicates an isocyanate
TABLE 1
__________________________________________________________________________
"A" Catalyst Temp. Reaction Product Ex. No. R.sup.2 moles (mole %)
.degree. C. Time (hrs.) Isocyanate MW EaW
__________________________________________________________________________
37 H 5 Bu.sub.2 SnO--4 100.degree. 6 -- 1240 -- 38 H 8 " " 4 --
1590 -- 39 H 15 " " 12 -- 2750 -- 40 H 5 " " 6 -- -- -- 41 H 8 " "
8 -- -- -- 42 --CH(CH.sub.3).sub.2 5 " " 6 -- -- 43 " 8 " " 8 -- --
-- 44 " 15 Bu.sub.2 SnO--5 125.degree.-150.degree. 1 I 4300 1488 45
" " " " " II 4000 1404 46 " " " " " III -- -- 47 " " " " " IV 3910
1380 48 " " " " " V 3960 1394 49 " " " " " VI 6170 1465 50 " "
Bu.sub.2 SnO--0.25 125.degree. 2.5 -- 1860 635 51 " " " " " II'
4000 1018 52 " 10 " " 2 -- 1300 445 53 " " " " " II' 2860 733 54 "
5 " " 3 -- 730 55 " " " " " II' 1720 448 56 " 5 " " " VI' 2754 508
57 " 13 " " 2.5 II' 3945 1005 58 " 5 NaOMe--0.25 " 8 VI' 1720 448
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Films were made with a selection of isocyanates as indicated in the
following Tables II and III and rudimentary properties determined.
Table II summarizes the results when the hydroxyoxazolidine
functional compounds are employed and Table III summarizes the
results when the bisoxazolidine compounds are employed. The
oxazolidine/.epsilon. -caprolactone//isocyanate hydrocurable
composition afford high solids, long pot life resins which cure in
the presence of atmospheric moisture to afford attractive, tough,
solid resistant coatings as shown by the viscosity, tack-free time
and film properties of the polymers.
Improved solution stability without an increase in tack-free time
is realized with the bisoxazolidine (i.e., isocyanate coupled)
resins. Similar results are observed with a selection of di- and
triisocyanates.
Pencil hardness scale extends from 6B (softest) to 5B, 4B, 3B, 2B,
B. HB, F, H, 2H, 3H, 4H, 5H, 6H, and 9H (hardest). The point of the
pencil is rubbed down on flint paper to a flat surface. The pencil
is held at 45.degree. to the surface to be tested and then pushed
across the surface. The rating is the hardest pencil that does not
break the film.
Garnder-Holdt Viscosity is a bubble rise comparison viscosity. The
sample to be tested is placed in a standard viscosity tube. The
sample is then compared to a series of standard liquids with
assigned letter values. The visocosity of the sample is the letter
value of the standard with the same bubble rise rate. The scale of
the standards runs from A-6 (lowest viscosity) to Z-10
(highest).
TABLE II
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(Oxazolidine/.epsilon.-Caprolactone//Isocyanate Polymers) (eq.
polyester/1 eq. isocyanate cast from xylene at 50% solids)
Composition Viscosity Film .epsilon.-Caprolactone (GH after .times.
Hrs.).sup.1 Tack Free Film Properties No. (moles)/OX (1 mole)
IC.sup.2 1 4 22 48 144 Min. Appearance Swelling.sup.2 Hardness
__________________________________________________________________________
1A 5/HEOX I' A2 A2 A2 A1 B 60 clear light <6B 2A 8/HEOX " A2 A1
A1 A1 C 60 hazy light 3A 15/HEOX " C D E F N 90 " mod. and "
lifting 4A 5/IPOX " A3 A3 A3 A3 A3 240 clear swollen " 5A 8/IPOX "
A2 A2 A2 A2 A2 240 " moderate " 6A 5/HEOX VI' S W .infin. -- -- 10
" v. slight H 7A 8/HEOX " T X .infin. -- -- 10 " " F 8A 15/HEOX "
.infin. -- -- -- -- 15 " " <6B 9A 5/IPOX " D D E E G 60 " " F
10A 8/IPOX " M P R S W 30 " " F 11A 8/HEOX I' A4 A2 B D I >24
hrs. v. poor moderate -- 12A 8/HEOX VI' A .infin. -- -- -- 120
clear slight <6B 13A 5/HEOX II' A3 A3 A3 -- A3 60 " v. slight F
14A 8/HEOX " A3 A3 A3 -- A2 120 " " 6B 15A 5/IPOX " A4 A4 A4 -- A4
120 " slight F 16A 8/IPOX " A4 A4 A4 -- A3 120 " " F Composition
Viscosity Film .epsilon.-Caprolactone (GH after .times. Hrs.).sup.1
Tack Free Film Properties No. (moles)/OX (1 mole) IC 1 4 22 48 144
Min. Appearance Swelling.sup.2 Hardness
__________________________________________________________________________
17A 5/HEOX IV' A4 A4 .infin. -- -- 30 clear slight -- 18A 5/HEOX
III' T .infin. -- -- -- 15 " " -- 19A 8/HEOX IV' A3 A3 A3 A2
.infin. 30 " " -- 20A 8/HEOX III' G .infin. -- -- -- 15 " " -- 21A
15/HEOX IV' A A B B .infin. 60 hazy " -- 22A 15/HEOX III' V X
.infin. -- -- 15 clear " -- 23A 5/IPOX IV' A4 A4 A4 A4 A2 30 " " --
24A 5/IPOX III' B D .infin. -- -- 15 " " -- 25A 8/IPOX IV' A4 A4 A4
A4 A3 30 " " -- 26A 8/IPOX III' B K .infin. -- -- 15 " " --
__________________________________________________________________________
.sup.1 Solution sealed in viscosity tubes under N.sub.2 .sup.2
After 30 minutes exposure to 2-hydroxyethyl acetate at room
temperature
TABLE III
__________________________________________________________________________
(Oxaxolidine/.epsilon.-Caprolactone/Isocyanate//Isocyanate
Polymers) (1 eq. coupled polyester/1 eq. isocyanate cast from
xylene at 50% solids) Polyester Viscosity Film Properties Film
.epsilon.-Caprolactone (GH after .times. hrs).sup.1 Tack Free No.
(mole) OX IC Isocyanate 1 4 22 48 144 (Min.) Appearance
Swelling.sup.2
__________________________________________________________________________
A 5 HEOX I' I' Al -- A A D 45 clear moderate B 5 " " " I -- S W
.infin. 15 " C 15 IPOX I' II' A A A A A 60 hazy slight D " " II' "
B B B B B 60 " " E " " IV' " A A A A A 60 " " F " " V' " B B B B B
60 " " G " " VI' " I I I I I 60 " "
__________________________________________________________________________
.sup.1 Solutions sealed in viscosity tubes under N.sub.2 .sup.2
After 30 minute exposure to 2-hydroxyethyl acetate at room
temperature
* * * * *